Synthetic resins and process of making same



Patented Apr. 21, 936

SYNTHETIC RESINS AND PROCESS OF MAKING SAME Theodor Sutter, Basel, Switzerland, assignor, by-

mesne assignments, to Clba Products Corporation, Dover, Del.

No Drawing. Application June 30, 1931, Serial No. 548,039. In Switzerland July 11, 1930 8 Claims.

- This invention relates to synthetic resins from primary aromatic amines and 'aldehydes. comprises the process for the manufacture of these resins, the new products themselves, as well a relatively low temperature and then reacting with formation of bodies which are very resistant to heat and chemical influence. However, there can also be added from the first a fiux in the sense of the British Patent Number 342,730. As

as the applicationof same in the industry of aldehydes uitable for the invention may be 5 synthetic resins. named para-formaldehyde, furfural, crotdnic al- It is known that by treating aromatic amines d yde, Pareldehyde, a d y salicylaldein presence of about the equivalent proportion y tollleheslllfosallcylaldehyde, thie alof a mineral acid with formaldehyde or a subyde 0 t e like. AS Substances y g aldestance yielding formaldehyde and subsequently hyde u ab e for t e nve o maybenamed fur- 10 separating the acid, both soluble and fusible and u d hexamethylene-tetlamlne, phenolinsoluble and infusible condensation products polyalcohols or the like. The last-named are can be obtained accordingly as a smaller or larger p ularly Suitable, because on the one hand proportion of aldehyde is brought into reaction. they enter into reaction V y low y nd on the Particularly valuable are the resins obtained- Other hand harden then quickly to a finished 15 from aniline and formaldehyde which are char- P d Combinations of amine resins containacterized by a surprising mechanical, electrical in; not much more than one mole ular Pr p and chemica] resistancg tion of formaldehyde with gradually reacting Further, in the British Patents Nos. 342,325 nts, such as furfura 0 ph n -p yalcohols and 342,723 there is disclosed thefact that the 501- or mixtures of e, w so eas ly and have such 20 uble and fusible resins obtained with at most one a high S ty at mode t p a ures that molecular proportion of formaldehyde can be they can be hardened in molds Without D converted by treatment with an aldehyde or a and fill even complicated molds Without substance yielding aldehyde into infusible resins leaving empty of essentially improved properthea The speed of the hardening may be still fur- 25 The present invention is based on the observather influenced by the addition of basic tion that this reaction is in no way limited to stances, such as furfuramide, triethanolamine or the condensation products with at most one mothe like or by lecular proportion of formaldehyde, ithaving The components may be mixed at any stage of been f d that the products with essentially the production. A particularly favorable condi- 30.

more than one molecular proportion of formaldetion 18 created by the fact that thB amine-formalhyde are profoundly changed in their properties dehydh'resihi when the acid is p ted, precip or improved by treatment with further quantities hates m a form having Such a large Surface nd of aldehyde or Substance yielding aldehyde. In high absorptive capacity that very considerable particular t t tendency of the resin t flow quantities of aldehyde soluble in water or sub- 35 .and the strength at raised. temperature and the stances y e d ng aldehyde are firmly retained, so chemical resistance of the finished products may that in the Washing pe at on n0 considerable be very strongly influenced, since, it being possi losses occur. In this manner a part cu a y 11111- ble to use gradually or rapidly condensing ald form dispersion can be obtained. If desired, the

40 hydes, or mixtures of aldehydes, there is at hand aldehyde o p enol-p lya co o ay be intro- 40 an extraordinarily wide range of the speed of duced into the acid condensation solution and hardening and stability of the new resins, It then the acid eliminated, or after the elimination appears, therefore, that the characteristic propthe acid the p ed m yd erties of the formaldehyde-amine-resinsare resin y b ed up With e hardening agent maintained even when relatively very large addio finally, the dry components may be united by 45 tions of other aldehydes and substances yielding mixing, grinding, melting together or like operaaldehyde are made. When one starts with con-' tion, the aldehyde, if desired, being diluted with densation products capable of being pressed at a solvent for the purpose of uniform distribution. high temperature, it is preferable to use high At any stage of the operation, if desired even at molecular aldehydes, which react gradually, or the first condensation, there may be added a fiux- 50 substances which liberate their aldehyde only at ing agent, a filler or another addition, such as a high temperature, for instance the phenol-polyhas been already proposed in the British Patents alcohol, these serving in the first phase as a flux Nos. 342,325, 342,723, 342,326 and 342,730. The and thus facilitating the pressing operation at ,mixing of the components in solution or suspension is particularly useful for homogeneous flxa- 55 tion of the resin on or in substrata, such as paper pulp, wood-meal, asbestos, paper or textile fabrics, which fixation can be conducted as described for amine formaldehyde-resins in the British Patents Nos. 284,589, 342,325, 342,723 and 342,326. The new products are applicable to many various purposes in the industry of artificial materials, for instance for insulating materials, for making useful and artistic objects of all kinds, as constructional material for machine parts or the like which must withstand a comparatively strong strain, for instance toothed guide wheels, parts of textile machines, such as spools or shuttles; also as material for packing joints, substitutes for wood in the furniture and building industries; finallyior gramophone records, loud speakers and other appliances for the acoustic industry.

The following examples illustrate the invention, the parts being by weight: 1

Example 1 93 parts of aniline (1 mol.) are dissolved in 100 parts of hydrochloric acid of 36 per cent. strength (1 mol.) in 200 parts of water. At a temperature of 25 C. there are added 79 parts of a formaldehyde solution of 40 per cent. strength (1.05 mol.) The temperature of the solution rises to about 35-40 C. and the colorbecomes a deep red. After about an hour the condensation thus produced is precipitated in the form of a thick magma by means of a solution of 40 parts of sodium hydroxide in 100 parts of water. It is filtered, washed until free from electrolytes and dried.

100 parts of the fusible resin thus obtained are ground with 30 parts of crotonic aldehyde. The powder can be pressed to form bodies which are infusible and of very good resistance to heat.

Example 2 100'parts of aniline (1 mol.) are mixed with 110 parts of hydrochloric acid of 36 per cent. strength (1.1 mol.) and 930 parts of water. There are then added 90 parts of formaldehyde of 40' per cent. strength (1.2 mol.) and the mixture, as soon as it has become orange to red, is stirred into 2000 parts of caustic soda solutionof 5 per cent. strength. There is precipitated a white to feebly reddish, voluminous powder which is washed and dried.

100 parts of the infusible resin thus obtained are ground with 20 parts of furfural. The reddish powder flows well under pressure and yields lustrous black forms of excellent properties.

Example 3 acid, 1.2 mol. formaldehyde are ground with 5 parts of para-formaldehyde and 2 parts of hexamethylenetetramine and the mixture is pressed. There are obtained forms having a high resistance to heat. Example 4 100 parts of an infusible resin obtained as described in Example 2 from 1 mol. aniline, 1.2 mol.

hydrochloric acid and 1.4 mol. formaldehyde, are ground with 10 parts of para-cresoldimethylol and 10 parts of furfural and the mixture is pressed. There are obtained homogeneous forms of excellent properties.

Example 5 100 parts of an infusible resin, made as described in Example 2, are thoroughly ground with s,oss,142

15 parts of para-cresoldimethylol and 1 part of salicylic acid and the mixture is pressed at 160 C. The powder, which flows well in the first stage of the pressing, hardens very quickly to a form which is very stable to heat.

. Example 6 93 parts of aniline are dissolved in the equivalent quantity .of dilute hydrochloric acid and the solution is stirred with parts of a formaldehyde solution of 38 per cent. strength for some time at 50 C. This solution is now poured into a mixture of phenol-polyalcohols, such as is obtained by allowing to stand for several days in the cold a dilute alkaline solution of 15 parts of phenol containing 2 equivalents of formaldehyde. The neutralization is completed with sodium carbonate solution and the whole is heated. if necessary to 60 C., and'flltered, and the solid matter is washed and dried. The powder thus obtained flows well and yields under pressure forms of very good stability to heat and resistance to fracture.

Instead of phenol as the parent material for the phenol-polyalcohols homologues of phenol or mixtures of these, para-dihydroxydiphenylpropane or the like may be used, in which case it may be advantageous to use more than 2 mol. formaldehyde for each 'phenol-hydroxyl.

Example 8 Into an acid condensation solution prepared from 93 parts of aniline, 600 parts of hydrochloric acid of 7 per cent. strength and 83 parts of a formaldehyde solution of 38 per cent. strength, there is run an alkaline solution of 20 parts of phenol-polyalcohol prepared as described in Example '7, and the whole is stirred for some time with 120 parts of wood meal. The greater part of the acid is then neutralized with caustic soda solution and the neutralization finished with sodium carbonate, whereafter filtration, washing and drying follow. The finely ground powderncan be pressed to filled forms of excellent properties.

Emample 9 parts of an infusible resin made as described in Example 2 are ground with 10 parts of an evaporated and dried condensation product from 1 mol. urea and 2 mol. formaldehyde. and the powder is pressed. The forms produced have high mechanical strength.

Example 10 2,ose,14a'

tives thereof which under the conditions of the condensation described herein, also act like the true primary aromatic amines under the conditions of.the present process to yield the same resins, for example,anhydroformaldehydeaniline,

formylaniline or the homologues of these compounds, and the like; 20

pounds as employed herein, is intended to cover not only formaldehyde itself, but its polymers or any other substances splitting oif formaldehyde or capable of forming methylene links under the conditions of the condensation, as it has been found that such substances or polymers may also be used in place of formaldehyde itself.

The term synthetic resinous material, as used in this specification and claims, is intended to cover not only the pure resin, but all forms in which such resin may occur, namely, resin solutions, molding powder, molded article, impregnated cellulose'material, in sheet form or loose, with or without the addition of fillers, plastiflers, coloring materials, and the'like.

What I claim is:

1. The step in the process of manufacturing synthetic resins from amine-formaldehyde condensation products obtained by reacting a pri mary aromatic amine with more than an equimolecular proportion of a formaldehyde yielding compound in the presence of a mineral acid and subsequently precipitating the product by an agent of alkaline character, which comprises adding a reactive aldehyde to the condensation product resulting from the reaction of the primary aromatic amine and the formaldehyde yielding compound in the presence of the mineral acid in any phase of the formation of said condensation product said aldehyde being adapted to impart hardened characteristics to said condensation product and being more slowly reactive with said amine than is said formaldehyde yielding compound.

2. The step in the process of manufacturing synthetic resins from amine formaldehyde conaniline than is said formaldehyde yielding compound.

3.'The step in the process of manufacturin synthetic resins from amine-formaldehyde condensation products obtained by reacting a primary aromatic amine with more than an equimolecular proportion of a formaldehyde yielding compound in the presence of a mineral acid and subsequently precipitating the product by an agent of alkaline character, which comprises adding furfural to the condensation product resulting from the reaction of the primary aropound in the presence of the mineral acid in any phase of the formation of said condensation product.

4. The step in the process of manufacturing synthetic resins from amine-formaldehyde condensation products obtained by reacting aniline with more than an equimolecular proportion of a formaldehyde yielding compound in thepresence of a mineral acid and subsequently precipitating the product by an agent of alkaline character, which comprises adding furfural to the,condensation product resultin'g'from the'reaction of the aniline and the formaldehyde yielding compound in the presence of the mineral acid in any phase of the formation of said condensation product.

5. A synthetic resinous material comprising a condensation product of a primary aromatic amine and more than an equimolecular proportion of a formaldehyde yielding compound obtained in the presence of a mineral acid, in intimate admixture with furfural.

6. A synthetic resinous material comprising a condensation product of aniline and more than an equimolecular proportion of formaldehyde ob- 'matic amine and the formaldehyde yielding comuct resulting from the reaction of the primary aromatic amine and the formaldehyde yielding compound in the presence of the mineral acid, said aldehyde beingadded in the substantial absence 'of unreacted amine and being adapted to impart hardened characteristics to said condensation product.

8. The step in the process of manufacturing synthetic resins from amine-formaldehyde condensation products obtained by reacting a primary aromatic amine with more than an equimolecular proportion of a'formaldehyde yielding compound in the presence of a' mineral acid and subsequently precipitating the product by an agent of alkaline character, which comprises adding furfural to the condensation product. resulting from the reaction of the primary aromatic amine and the formaldehyde yielding compound in the presence of the mineralacid, said furfural being added. in the substantial absence of unreacted amlne.

'I'HEODOR su'rrnn. 

